Certain polyepoxide-modified oxyalkylated phenol-aldehyde resins and method of making same



United States PatciitiQ 2,854,428 CERTAINTOIJYEPQXIDEZMQDHIED OXYALKYE ATED PHENOL-ALDEHYDE RESINS AND METH- 01) OF MAKING SAME MelvinDe Groote, St. Louisy and Kwan-"l ingnshen, Brentwood, Mo., assignbrs to P'etrolite Corporation,

Wilmington, DeL, a corporation of Delaware 6 Clainisi cl..'-260-43 This application is a division of our co-pending application Serial N6." 34'9,9=72, 3 fiIed A riI ZOZ1958; now Pat. No. 2,792,353.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularlyadapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the-- application of such chemical products or compounds in. various other arts. and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsificatio'n.

The products of our invention are synthetic hydrophile products obtained by the reaction of certain oxyalkylated-phenol aldehyde resins, hereinaiterrdescribed-in detail, "with certain non-aryl hydrophile polyepoxides; also hereinafter described -in.-detail.-.-

The products previously described which are obtained by reaction between -a polyepoxide and certainoxy-- alkyla-tionderivatives are use-ful for various purposes 'in.-- eluding-.- the-resolution-of petroleumemulsions --of the water-imoil type,- are obtained -fr-om -cer'=t'ain heat-stable re'sins,=whieh; since they areheat-stable, are also suscepvi; tible to-i-reac'tion in:various-ways to yield productsiother? than oxyalkylation products, such as amine: derivatives:- Such aminc derivatives-may be obtained,' -for example by subjecting the resins td -reaction with ethyI'ene-"ii'riine,- propylene imine, *or similar "iriliii'es 'ra'tlier than reaction with ethylerle 'ozidefipropyleneoiride, etc. cb'mparaeie compounds-are obtained by derivatives which, iii addi tibri to havingftlie "iminfia'dic'alj' have"a1r ether linkage such as 1 wl'li'c'li" have not een? subjected to the intermediate re-- action-"with arr-imine.

Actually any reference hr the claims-on specification:-

to the property. of; bein-g "oxyalkylation-susceptible might just as properly be-characterized-as bein'gfiimine so obtained are" 2,854,428 Peftented Sept. 30, 1958 21 reactive'or for that matter as oxyalkylation-susceptible and imine-reactive.

The products obtained-by reaction. between the oxyalkylatedderivativesand the polyepoxides: are obviously acylation-susceptible as well as being oxyalkylationsusceptible. For instance, they could be subjected to reaction with alkylene oxides different than those previously described, as for example, styrenexoxide. These derivatives additionally must. have'a" number of aliphatic hydroxyl groups. Such aliphatic hydroxylgroups as differentiated from phenolic hydroxyl groupsprescnt in one of the initial reacta'nts areparticularly susceptible to acylation with various carboxylic and non-carboxylic acids. They may be reacted with detergent-forming monocarbox y acids, particularly higher fatty acids, which are saturated or unsaturated, as well as polycarboxy acids, such as phthalic anhydride, maleic anhydride, etc. Similarly-,5 they-can-be reacted'withmaleicvacidc or a fractional rnaleic add i ester; such 5 as: the monooctyl ester ofi maleic'acidpandvthe neutralwester obtained can.:be reacted-with sodium: bisulfiteso as:to introduce a- 'sulfonic group;

The" present inventionis characterized by the use of compounds derived fronr' dig'ly cidyl ethers which do not introduce anyhydrophbbe properties in its usualmean ing' 'but"in:: fact? are moreapf'to introducet"-hydrophile properties. Thus, the; die'p'oxi'de's employed in'the' present invention are characterized by .the fact that the divalent radical connectingthe terminal epoxide radicals contains less than 5: carbon atomsin an :interruptedchain'.

The-diepoxides employed in the present processnare obtained'fromglycols such as ethylene glycol diethyleneglycol,v propylene glycol, -dipropylene glycol, tripropyleneglycol; butylene glycol, dibutylene-glyco1; .tributylene-, glycol, glycerol, diglycerol, triglycerohand similar com; pounds. Suchproducts. are well known-randare-characterized by'the fact that there are not more' than' 4 un interrupted carboni atoms in anygroup--which is part= of 'tlie 'radi'cal joining the epoxidc groups. 0P necessity such diep'oxides' must" be non-aryl or" aliphatic in"'charac-, terl The diglycidyl ethers of our co-pendingapplication,'Serial No. 324,814, filed December 8, 1952, are invariablyand "inevitably aryl in character.

The diepoxides employed in the present: process .are usually obtained-by reactinga glycol or-equivalent compound,- such as glycerol or diglycerol with epichloro hydrinrand subsequently with 'an alkali. Such E'diepoxides have been described in the literature and: particularly, the patent'literature. See, for example; Italian Patent 400,973,dated August 8, 1951'; see-,w also, aBritish Patent 518,057,;dated-December 10, l938;-and=.U.S. Patent 'No; 2,070,990,;datedFebruaryl6, 1937 'toGroll ct al-.l Refer-.- ence-is-':made also to U. S. Patent No; 2,581,464, dated January :8;- 1952, to Zech. This particular last rnentioned patent describes: :acomposition of r the following; general formula in which xis at lastl, z variesfr'om less than lto more than 6, and R is the residue of the polyhydric Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with a resin as described. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethylene-glycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxide rings or oxirane rings in the alphaomega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest dicpoxide which contains at least 4 carbon atoms and is formally described as 1,2- epoxy-3,4-epoxybutane (1,2,3,4 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed toward products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. of illustration to show a typical diglycidyl ether of the Simply for purpose:

' rings as depicted 4 kind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only six atoms thus:

non

Ho-o-on Commercially available compounds seem to be largely to the former with comparatively small amounts, in fact comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy in the next to last formulapreceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any oxyalkylated phenolaldehyde resin by virtue of the fact that there are always present either phenolic hydroxyls or their alkanol radicals or the equivalent or alkanol radicals in the presence of any phenolic hydroxy Indeed, the'products obtained by oxyalkylation of the phenolic resins must invariably and inevitably be oxyalkylation-susceptible.

To illustrate the products which represent the subject matter ofthe present invention, reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and an oxyalkylated resin. Proceeding with the example previously described, it is obvious the reaction ratio of two moles of the oxyalkylated resin to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

E (0K)! (0K), H,CC-O O- 1-- Ih-O-C-C-CHI H: H:

Oxyalkylated resin) (Oxyalkylated resin) in which n is a small whole number less than 10, and usually less than 4, and including 0, and R represents a divalent radial as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization oxyalkylated resin is simply an abbreviation for the oxyalkylated resin which is described in greater detail subsequently.

Such products must be soluble 'in suitable solvents such as a non-oxygenated hydrocarbon solvent or an oxygenated hydrocarbon solvent or, for that matter, a mixture of the same with water. Needless to say, after the has been treated with a large amount of ethyleneoxid'e, the products are water soluble and may be soluble in an acid solution.

The: purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from. relation or cross-linking. Not only does this property serve to differentiate from the instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct Water-solubility or are distinctly soluble in 5% acetic acid For instance, the products free from any solvent can be shaken with five to twenty times their weight of distilled water at ordinary temperature and are at leastself-dispersing, and in many instances water-soluble, in fact, colloidally soluble.

Basic nitrogen atoms can be introduced into such derivatives by use of a reactant having both a nitrogen group and a 1.,2-epoxy group, such as 3-dialkylaminoepoxy propane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsionsof the water-in-oil type, and also for that matter for numerous other purposes" where surface-active materials are effective, and particularly for those uses specified elsewhere herein, we prefer to employ oxyalkylated derivatives, which are obtained by the use of. monoepoxides, in such manner that the derivatives so obtained have sufiicient hydrophilecharacter to meet at least the test set forth in U, S. Patent No. 2,499,368, dated March 7, 1950,-to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkyl'ated derivatives obtained particularly by use of ethylene oxide, propylene oxide, etc., may not necessarily be xylenesoluble although they are xylene-soluble in a large number of instances. If such compounds are not xylene-soluble the obvious chemical equivalent, or equivalent chemical test, can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test obviously is the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Another peculiarity of the compounds herein described is that they may pass into a comparatively high molecular weight range and be efiective for various purposes, not only for the resolution of also for other industrial uses described in detail else- Where. This characteristic may be related to the fact that the initial resin molecule, obtained in turn from two resin molecules combined by means of a polyepoxide as described, results in a fairly large molecule.

As previously pointed out, we have found that we can obtain effective compounds for the herein described purposes where surface-active materials are employed, Whether it be for the resolution of petroleum emulsions or other uses, in which the oxyalkylated derivatives subjected to reaction with a polyepoxide may represent roughly two parts of the initial resin and 98% of the alkylene oxide. The word, oxyalkylated, is employed in this sense for the purpose of convenience in referring to the monoepoxide derivative only.

For purposes of convenience, what is said hereinafter will be divided into six parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides, and particularly diepoxides, employed as reactauts.

petroleum emulsions but :2 is eoncerned with suitable phenolaldehyde resins to be employed for-reaction with r the epoxidesi Part 3 is concerned with-the oxy r ylati'on of the previously described phenol-aldehyde resins. r 5

4 is concerned with-reactions involving-the two preceding typeof materials and examples obtained by such reaction. Generally speaking, this; involves nothing more a reaction between two moles of a previously prepared oxyalkylated phenol-aldehyde resin as; described and one mole of a polyepo-fde so as to yield anew and larger oxyalkylated" resin molecule. I

Part 5 is concerned with'the resolution ofpetroleum emulsions of the water-mgoil type by means of'thepreviously described chemical compounds or reaction products; and

Part 6 is concerned; with uses for the products herein described, either as such or after modification, including uses in applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 7 Reference is made to previous patentsillustrated in the manufacture of the non-ariyl -polyepoxides and particularly diepoxides employed as reactants in the instant invention. The simplest diepox'ide is probably the one derived from 1,3-butadiene orisoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglyci'dylethers may be indicated thus: 1

In some instances the compounds are essentially derivatives of etherize'd epichlorohydrin or methyl epichlorohydn'n. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned'U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following The diepoxides previously described may be indicated by the following formula:

In another example pre- However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide 'is'obtained from diglycerol which is largely acyclic diglycerol, andepichlorohydrin or equivalent thereof, in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy, rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical theoxygen atom that was derived from, epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R, is selected from groups such as the following: f

imo im czm r o a' c r a i a It is to be noted that in the above epoxides there is a complete absence of (a) aryl radicals and (b) radicals in which 5 or more carbon atoms are united in a single uninterrupted single group. R is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol HOROH must be watersoluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by Thus, R(OH),,, where n represents a small whole number which is 2 or more, must be water-soluble. Such limitation excludes polyepoxides if actually derived, or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to carbon atoms or thereabouts.

Referring to a compound of the type above in the formula in which R is C H (0H)', it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, ifR happened to be C I-I (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether, free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of .the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethylone-glycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polycpoxides, and particularly diepoxides, to differentiate from comparable and compounds, is to use the terminology epoxyalkanes and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difiiculty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

PART 2 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications: said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U. S. patents: Nos. 2,499,365; 2,499,366; and 2,499,367, all dated March 7, 1950 to- De Groote'and Keiser. These patents, along with the: other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbonatoms are most satisfactory, with the additional C carbonv atom. also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at lea-st at the present time.

Patent 2,499,370 describes in detail methods. of preparing resins useful as intermediates for preparing the products of the. present application, and reference is made. to that patent for such detailed description and to- Eiratnples' 1a through 103a. of that patent for examplesofi Suitableresins.

As previously noted, the hydrocarbon substitIYe nt in the: phenol may have as manyas 18 carbon atoms, as: illustrated by tetradecylphenol, hexadecylphen'ol and: octad'ecylphenol reference in each instance being to the: difunctionalphenol, such asthe orthoor para-substituted phenol; or a mixture of, thesame; Such resins aredescribed also in issued patents, for instance, U. 8;. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

It is sometimes desirable to present the resins herein employed in an over-simplified form which has appeared from time to time in theliterature, and. particularly in thepa tent literature, for instance, ithasbeen statedthat' the. composition is approximated in an idealized form by the formula OH OH OH HF H] R R n' in the: above formula n represents. a small whole number.

varying from 1 to: 6, 7 or 8', or more, up to probably 10 50.

or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. Alimited: subegcnuslS. in.the: instance of low molecular Weight polymers where the. total number of phenol nuclei varies; from 3' to 6, i. e., it varies from 1- to4; R' represents an aliphatic hydrocarbon substituent, generally an.

. alkyl radical having from 4 to 14 carbon atoms, such' as butyl; amyl,. hexyl, decyl or dodecyl' radical. Where: the-divalent bridge radical is shown. as being derived from formaldehyde, it may, of? course, be'derived from 22a...

any other reactive aldehyde having 8- carbon atoms or less.

In. the. above formula the aldehyde employed in the resin manufacture is formaldehyde. other aldehyde such as acetald'ehyde, propionald'ehyde, or butyraldehyde' may be used. The resin unit can be exemplified thus:

Actually, some H yL To in which R'" is the divalent radical obtained from the particular. aldehyde. employed. to. form.- theresin.

Resins bemade using: an acid catalyst. or basic catalyst. or' a: catalyst. showing neither acid nor basic. properties-im the. ordinary sense or without: any-catalyst atall. It is'preferablethat the resinsemployed bessub= stantially neutral. Imother words, ifprep'ared by-using astrong; acid. as a. catalyst, such. strong. acid. should. be neutralized. Similarly, if astrong base is; used; are a, catalyst it. ispreferable that. the base be: neutralized although. we have found thatsmnetimes the-reaction dee; scribed. proceeded more rapidly. in the presence of? a smalluamountof a free-base. The amount may be: as small as a 200th of a percent. and-as much as; w few 1.0.0ths. of as percent. Sometimes moderate. increase: in caustiesoda and. causticlpotashmay. ;be=used; However-,, the. most: desirable. procedure. impractically, every, case; is: to have the resin neutrahw In preparing; resins oneadoes not. get. aminglepolymer, i.- e.,..one: having just 3 'units; or just. 4. units, orjust units,. or just. 6.-'units,. etc.. It is. usually a mixture; for; instance, one approximating 4-: phenolic. nucleiwill. have some trimen andpentamer. present. Thus,.the. molecular. weight may be such that it corresponds. to a. fractional: value for; n as; for. example,, 3.5;. 4.5;. or 5.2.

In. the-actual manufacture of: the resins we. found no. reason: for using, other. than. those. which. are-lowest. im price and. most. readily available. commercially; Eon purposeof convenience: suitable resins. are characterizedl in-the: followinglable:

TABLE L Ex, R amplea R Position derived at number of R from Tertiary butyl Para Formal- 3; 5.

Secondary butyl. Ortho... 3. 5. Cyclohexyl. Para. 3; 5. Tertiary amyl. do 3.5: .Mixedtsecondary 0rtl10 3; 5. and tertiary amyl.

Propyll 3.5. .Tertiary hexyL. 3:5 .OctyL. 3.5. 3.5.

13a Tertiary amyl do.- 3- 5. 14a 'Nonyl do do 3.75. ;Tertiar.y butyl do Butyr- 3:5.

; aldehyde 1fia Tertiary amyl do 3. 5: 17a nyl 3. 5.? 18a Tertiary butyl 3J5 19a zlertiary amyl 3. 5 20a -N0nyl; 31 5. 21c Tertiary butyl' 4.2:.

. 4.12 4.12 4.:8. 4.8 2611 4.;8. 27a 11 11 29a... .1: a j 1.

11 PART 3 There have been issued a substantial number of patents which give detailed description of the preparation of oxyalkylated derivates of resins of the kind previously described. For example, see U. S. Patents 2,499,365; 2,499,366; 2,499,367; 2,499,368; and 2,499,370, all dated March 7, 1950 to De Groote and Keiser.

More specifically, a number of other patents have appeared in which the oxyethylation step is given with con siderable detail. See, for example, U. S. Patents 2,581,- 376; 2,581,377; 2,581,378; 2,581,379; 2,581,380; and 2,581,381, all dated January 8, 1952, to De Groote and Keiser. As to further examples, see U. S. Patent 2,602,052 dated July 1, 1952, to De Groote.

The oxypropylation or, for that matter, the treatment of resins with butylene oxide, glycide, or methyl glycide, has been described in the first of the series in the abgve mentioned patents, i. e., those issued in 1950.

Reference is made to U. S. Patent 2,557,081 dated June 19, 1951 to De Groote and Keiser. This particular patent describes in considerable detail resins which are first treated with propylene oxide and then with ethylene oxide or with ethylene oxide and then propylene oxide or with both oxides simultaneously.

In order to avoid an extensive repetition of what is already described in detail in the patent literature, we are referring to the tables beginning in column 21 of U. S. Patent 2,581,376 and extending through column 36. We have simply numbered these products beginning with lb, allotting, of course, five numbers to each table beginning with the first table. For convenience these sixteen tables are summarized in the following tables:

TABLE II 801- Eth- Exam- Phenol Aldehyde vent, Resin, ylene ple No 5. lbs. oxide,

lbs

10 Para-tertiary amyl. 14. 75 4. 20. d0 10. 15.25 3!) 7. 93 19. 69 3. 25 16. l. 04 10. 15. 00 8. 00 10. 00 9. 40 7. 27 13. 70 3. l5 8. 95 2. 10 8. 00 14. 80 3. ll. 40 12. 6. 36 15. 4. 90 14. 4. 58 18. 13. 10. 00 5. 58 4. 3. 14.

TABLE II-Gontinued Sol- Eth- Exarn- Phenol Aldehyde vent, Resin, ylene ple N0 lbs. lbs oxide,

lbs.

51b Para-secondary 20.75 520 15.85 530 11.25 541) 8.52 550 4. 93 56b 57b 9.00 58b Para-phenyl Para-secondary ear in the above tables in U. B.

NOTE.-F0! ease of comparison, blanks ap table where blanks appear in previously mentione Patent 2,581,376.

TABLE III Ex-1 Oxy- 801- R Proampe propyvent, esin, py eue o. lated Phenol Aldehyde lbs. lbs oxide,

analog lbs 10 1b.. Para-tertiary Firmialde- 14.25 15.75 5.10 10.90 12.10 19.40 7.13 7. 93 25.30 3.84 4.25 23.00 1. 2.04 13.00 13.30 16.90 3.82

As an illustration of oxypropylated resins involving the use of both ethylene and propylene oxide, a reference is made to the aforementioned U. S. Patent 2,577,081, dated June 19, 1951, to De Groote and Keiser. The last table in column 28 of said patent describes in detail the preparation of a series of oxyalkylated resins in which both propylene and ethylene oxide are employed. Simply by illustration, a series of 27 compounds are included, the description of which appears in detail in said aforementioned U. S. Patent 2,577,081,

, to De Groote and Keiser.

TABLE m 1 See U.,S.Pat. p I 2,557,0s1- v Ethylene Bropylene; Flake Ex. No. Point Resin used Resin, oxide, oxide, Weight caustic Ex.No. on l lbs; lbs. lbs. oixylene I soda,

1 graph unces above on patent .above.

I B 4 1 C 3 6 t 1 a l D 1 21.5 2, 5, 25 2. E 1 9 j 2 I= 6 1 3a 10 1 A 6 I 3 1- 10 l B 5 4 1 1o 1 o a: t 6 t 1 10; 1 V D. 1 21.5 as j 25, 2. E 1 15 9 25 2, E: 1: i 10 14 25 t 2 G- 1;. I 2.6; 21,.51 25; 1 2 H o 1 4 10 1 I 6 1 3 10 t 1- A, e s 1E 10-; 1., B s 4 1 1Q 1 O 3 I 6 v 1 10 1'- D 1 3 2'5. 2 F E 1 15 9 25 2 F 1 10 14 25 2 G 1 Y 2.5 21.5 25 2 H 5 1 4 10-- 1, I 6 1 3 1O 1,

Note the first series of nine compounds, ld through BART4 9d were prepared, With, propylene l e, first 311d. then Aspreviously stated, the final stage reactions involve ethylene Q e-. Th seeond nille p l 11 1 .8 ztwo moles .of an oxyalkylated phenolealdehyde resin of 1 18d inclusive, WerePIePafed 115mg ethylene: OXlde r t n the kind previously described; and one mole; ofa diglycidyL then P py Oxide, and h t nine cmr d ;2d ether as s ecified. The reaction is essentially an. oxyalkylthrough 27d, Were! p feffilr d y rg oxyelkyleflon, ation reaction and thus maybe considered as merely a coni. e., using a mixtureo etwo oxies. tinuance of; the previous: oxyalkylation reaction in- In the preparation of the resins, our preference is to.use volving a monoepoxide as, diiferentiated from a polyepoxhydrocarbon S it phe p i l r y P E-e-t l 'ide and particularly a diepoxide. The reactions take stituted, in which the substituted; radical R contains, 4 bplace i i bstantially. the same way, i. e.,, by the opporto 18 ar on a s'an p i a y cer omstunity to, react at somewhere abovethe boilin point of Th am n o alkylene Oxide I'HtIOdIICedFmaY 0 water andj below the point of decomposition, for example, paratively large in comparison t h l: resint FQ 130 185 C. in the presence of a small amount of a1- instance, there y be as much 50 P S Y t of kaline catalyst. Since the polyepoxide is non-volatile as an oxi e r m d oxides u for each par y igh com ared, for example, with-ethyleneoxide, the reaction of resin employed. is comparatively simple. Purely from a mechanical stand- It will be noted that he rio s resins referred in point it is a matter of convenience to conduct both classes the aforementioned U. S. Patent 2,499,370 are substanf tio s in the same equipment. In other words, t-ially the same type of materials as referred; to in Table I. ft the, phenol-aldehyde r in. ha b en r acted with For instance, resin 2a of the table is substantially the same ethylene oxI-ide, propylene oxide or the like, it is subseas 2 0f the P resin 0f e: table is b ti ly quentlyreacted with a polyepoxide'. Thepolyepox-ide-rethe same as 34a of the patent; and resin 37a of the table is a ti n a be conducted in an ordinary reaction; vessel the same as 3a of the patent. suchias the usual' glass laboratory equipment Thisis In reaction with polyepoxides, and particularly diepoxparticularly true ofthe-kind'used' for resin manufacture ides, a large number o the pr y ri c yas described ina number of patents, asfor exam le,

alkylated resins have been employed. For. convenience U. S: Patent No. 2,499,365. One can use a variety; of the following li t is s l d ing h pr vio s y catalysts in connection with the-polyepoX-ide ofthesame described compounds and their molecular weights. Such class employed with monoepox-ide. In fact,the reaction resins are generally employed as a 50% solution and the will go=at an extremely slow rate without any catalyst at polyepoxide employed is a 50% solution, usually both all; The usual catalysts includealkaline materials such reactants being dissolved in xylene and suflicient sodium as'caustic soda, caustic potash, sodium methylate, etc. methylate added to act as a catalyst,.for. instance, 1 to.2% Other catalysts may be-acidic in nature and are ofthe-kind characterized by iron and tin chlorides; Furthermore,

TABLE insoluble catalysts such as clays or specially prepared mineraL catalysts, have beenv used. For practical; pur- Example number Mgegglsar Example number Mglggglzar poses, itv is best tou'ser the samg catalystas is used the ni i l o y ky at ep n many a es. he e-is. ute

5 ficient residual catalyst to serve forthe reaction myolying 1,202 N 2,169. 6,139 the second oxyalkylatlon step, 1. e., thepo1yepox de. For; 2: Z; this, reason, we. have preferred to use a small amount: of 5,749 1; 91s finely divided; caustic soda or sodium methylate as the; g; ,3; initial catalyst and also, the catalyst in the. second: stage; 9 9 The amount generally employed is, l, 2, or 3% of these 5,867 24,909

6,087 23;!159 alkal n catalysts.

1, Actually, the reactions of pplyepoxides. with various resin materials. have been thoroughly described int the 15 literature and the procedure is, for all purposes, the same as with glycide which has been described previously.

It goes without saying that the reaction involving the polyepoxide can be conducted in the same manner as the monoepoxide as far as the presence of an inert solvent is concerned, i. e., one Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The solvent so selected should be one which, of course, is suitable in the oxyalkylation step involving the monoepoxides described subsequently. The solvent selected may depend on the ability to remove it by subsequent distillation if required. Here again it has been our preference to have a solvent present in the oxyalkylation involving the initial stage and permitting the solvent to remain. The amount of solvent may be insignificant, depending whether or not exhaustive oxypropylation is employed. However, since the oxypropylated phenol-aldehyde resins are almost invariably liquids there is no need for the presence of a that is not oxyalkylation-susceptible.

r the diepoxide was added the to approximately 109 diepoxide was approxixylene, were added. Afte temperature was permitted to rise C. The time required to add the mately one-half hour. The temperature rose in this period to about 127 C. The temperature rise was controlled by allowing the xylene to reflux over and to separate out the xylene by a phase separating trap.. In any event, the temperature was raised shortly to 148-150 C. and allowed to reflux at this temperature for almost three hours. Tests indicated that the reaction was complete at the end of this time; in fact, it probably was complete at a considerably earlier stage. The xylene which had been separated out was returned to the mixture so that the reaction mass at the end of the procedure represented about reaction product and 50% solvent. The procedure employed is, of course, simple in light of what has been said previously; in fact, it corresponds to the usual procedure employed in connection with an oxyalkylating agent such as glycide, i. e., a non-volatile oxyalkylating agent. At the end of the reaction period the mass obtained was a dark, viscous mixture. It could be bleached, of course, by use of charcoal, filtering earths, or the like.

Various examples obtained in substantially the same manner as employed are described in the following solvent as when oxyalkylation involves a solid which 25 tables:

TABLE VI Ory- Catalyst Time of Max. Ex. alkyl- Amt, Dlepox- Amt., (N 9.0GHz), Xylene, Molar reaction, temp, Color and physical state No. ated gms. ide used gms. grams gms. ratio hrs. O.

resin 217 11 1s. 5 1.1 235. 5 2:1 3 150 Dark, viscous mass. 400 A '13. 5 2. 3 47s. 5 2:1 4 155 Do. 247 .A. 18. 5 1. 3 255. 5 2:1 3 152 Do. 509 A 18.5 3.1 527. 5 2:1 5 158 Do. 249 A 18. 5 1. 3 257. 5 2:1 3 Do. 402 A 18.5 2.1 420. 5 2:1 4 Do. 708 A 18. 5 3. 6 720. 5 2:1 5 Do. 192 A 18. 5 1. 0 210. 5 2:1 3 150 Do. 319 .1 1s. 5 1. 5 337. 5 2:1 3 152 D0. 249 .4 1. 9 1. 2 251.0 2:1 3 155 Do. 217 B 11.0 1. 1 22s. 0 2:1 3 148 Do. 400 B 11.0 2. 3 471. 0 2:1 4 150 Do. 247 B 11.0 1. 2 25s. 0 2:1 3 145 Do. 509 B 11.0 a. 1 520. 0 2:1 5 155 Do. 249 B 11. 0 1. 3 250 2:1 3 142 Do. 402 B 11.0 2. 0 413 2:1 4 150 Do. 708 B 11.0 3. 5 719 2:1 5 155 D0. 192 B 11.0 1.0 203 2:1 3 148 Do. 319 B 11.0 1. 6 330 2:1 3 150 Do. 249 B 1.1 1.2 250 2:1 3 150 D0.

may be rather high melting. Thus, it is immaterial wheth- TABLE VII er there is solvent present or not and it is immaterial whethersolvent was added in the first stage of oxyalkyla- Probable tion or not, and also it is immaterial whether there was 5() i gfi 23K 3 333, 3 3? 3, solvent present in the second stage of oxyalkylation or not. used 18295101? grams grams The advantage of the presence of solvent is that somepm times it is a convenient way of controlling the reaction 4, 710 4, 710 2, 355 temperature and thus in the subsequent examples we have 9, 570 4,785 2, 390 added sufiiclent xylene so as to produce a mixture which 3. 2 3 3g boils somewhere in the neighborhood of 125 to 140 C. 5:350 5:350 2:675 and removes xylene so as to bring the boiling point of the 8 g *;.;%2 @1 32 mixture to about 140 C. during part of the reaction and 210 210 21100 subsequently removing more xylene so that the mix ture g, refluxed at somewhere between to C. ThlS 4:560 1: 21280 was purely a convenience and need not be employed unguig {g3 less desired. 2, 200 100 Example 1e 31388 213% 31% The oxyalkylated resin employed was the one previ- 14,380 71190 31590 4, 050 4,050 2,030 ously identified as 2b, having a molecular weight of 2169; 6,600 6, 600 3,300 the amount employed was 217 grams. The resin was dis- 50,040 5, 009 solved in approximately an equal weight of xylene. The mixture was heated to just short of the boiling point of PARTS water, i. e., a little below 100 C. Approximately one half percent of sodium methylate was added, or, more exactly, 1.1 grams. The stirring was continued until there was a solution or distribution of the catalyst. The mixture was heated to a little past 100 C. and left at this temperature while 18.5 grams of the diepoxide (previously identified as A), dissolved in an equal weight of Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly, aliphatic alcohols, such as methyl alcohol, ethyl alcohol,- denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed With one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents maybe used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of our invention when employed as demulsifying agents.

The materials of our invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, .and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and doWn-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 10, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulionic acid, 12%;

A high-boiling aromatic Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 6 The products, compounds, or the like herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the waterin-oil type as described in detail in Part 5 immediately preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine, one may employ what is somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure petroleum solvent,

RI! wherein R and R" are alkyl groups.

It is not necessary to point out that after reaction with a reactant of the kind described which introduces a basic nitrogen atom that the resultant product can be employed for the resolution of emulsions of the water- 18 in-oil type as described in Part 5, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part 4 preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from pctroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected, and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions in so far that demulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosive inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-inwater emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent, is:

l. The method of reacting (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a non-aryl hydrophile polyepoxide containing at least two 1,2-epoXy rings and having two terminal 1,2-epoxy rings obtained by replace ment of an oxygen-linked hydrogen atom in a watersoluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present up to 20 carbon atoms; said oxyalkylated phenol-aldehyde resins reactant (A) being the products derived by oxyalkylation involving (aa) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide, and ([211) a fusible, organic solvent-soluble, Water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an in which R is a saturated hydrocarbon radical having not more than 24 carbon atoms and substituted in the 2,4,6 positiofii Said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O),,, in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 120; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of two moles of (A) to one mole of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solventsoluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

2. The product obtained by the method defined in claim 1.

3. The method of reacting (A) an oxyalkylated phenolaldehyde resin containing a plurality of active hydrogen atoms, and (B) a non-aryl hydrophile diepoxide containing two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a watersoluble polyhydric alcohol by the radical H H H 'g.C\-7CH said diepoxides being free from reactive functional groups the tha Isl-e x and ydrexfl groups a a terized by the fact that the divalent linlgage uniting the terminal xiran n s s re fwm y a i a n more than 4 uninterrupted carbon atoms in a single chain; said diepoxides being characterized by having present up to carbon atoms; said oxyalkylated phenolaldehyde resins reactant (A) being the products derived by oxyalkylation involving (aa) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide, and (bb) a fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; saidrresin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated hydrocarbon radical having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O),,, in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, hydroxypropylene hydroxypropylene radicals, and hydroxy-butylene radicals, and n is a meral varying from 1 to with the provisothatatleast 2 moles of alkylene oxide be introduced for each'phcnolic nucleus, and that the resin by weight represent'at least 2% of the oxyalkylated'derivative; the ratio of reactant- (A) to reactant (B) being in the proportion ot two moles of -(A) to one mole of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nontherrnosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the react-ion product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted belowthe pyrolytic point of the reactants and the resultants ofreaction.

4. The method of claim 3 wherein the diepoxide contains at least one reactive hydroxylradical.

5. The method of reacting (A) an oxyalkylated phenolaldehyde resin containing a plurality of active hydrogen atoms, and (B) a hydroxylated diepoxy polyglycerolcontaining two terminal 1-,2-epoxy rings and havingup to 20 carbon atoms; said oxyalkylated phenol-aldehyde resin, reactant (A) being the product derived by oxyalkylation involving (aa) an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycidc, and (bb) a fusible, organic, solvent-soluble, water-insoluble phenolaldehyde resin; saidresin being derived by reaction be tween adif-unct-ionalmonohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence oftrifunctional' phenols; said phenol; being of; the formula in which R is a saturated hydrocarbon radical having not more than 24 carbon atoms andsubstituted in the 2,4,6 position; said oxyalkyl ted resin being characterized by the introduction into the resin moleculefof a pluralityradicals, and hydroxybutylene radicals, andyn is a numeral varying from 1 to 120; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (1A) .to reactant (B) being in the proportion of two molesof (A) to one mole of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non -thermosetting organic solvent-soluble liquids and s olids melting below the point of pyrolysis; with thefinal proviso that the reactionproduct bev a member of the class of solyent-solubie liquids and solids melting belowv the point of: pyrolysis; and-said reaction between (A) and. (B) beingcondncted below the pyrolytic point of the reactants and the resultants of reaction.

6. The method of claim 5 wherein the polyglyccrol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substitucnt group, and the precursory aldehyde is formaldehyde, and the total number of phenolic nuclei in the initial resin is not over 5.

De Groote ct al. Feb. 28, 19 50 Greenlee Sept. 12, 1950 

1. THE METHOD OF REACTING (A) AN OXYALKYLATED PHENOL-ALDEHYDE RESIN CONTAINING A PLURALITY OF ACTIVE HYDROGEN ATOMS, AND (B) A NON-ARYL HYDROPHILE POLYEPOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS AND HAVING TWO TERMINAL 1,2-EPOXY RINGS OBTAINED BY REPLACEMENT OF AN OXYGEN-LINKED HYDROGEN ATOM IN A WATERSOLUBLE POLYHYDRIC ALCOHOL BY THE RADICAL 